Polyorganosiloxane resins with release effect

ABSTRACT

The present invention relates to compositions for preparing coatings having a release effect, to substrates coated therewith, and to a process for preparing the compositions.

RELATED APPLICATIONS

[0001] This application claims priority to German application 199 34 103.6, filed Jul. 21, 1999, herein incorporated by reference.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to compositions for making coatings having a release effect, to substrates coated therewith, and to a process for preparing the compositions.

[0004] 2. Description of the Related Art

[0005] Coatings based on silicone resin and silicone oil, and their use as release coatings, have long been known. For instance, U.S. Pat. No. 2,606,510 describes the use of silicone resins, U.S. Pat. No. 2,462,242 the use of silicone oils.

[0006] The use of hydroxy-functional polymethylphenylsilicone resins for release coatings on baking trays is described in U.S. Pat. No. 2,672,104.

[0007] The combination of silicone resins and silicone oils for release coatings has been used in practice for a number of years. Combinations of this kind are particularly suitable owing to the release effect for a wide range of foodstuffs and owing to the good resistance properties. An example is the combination described in U.S. Pat. No. 3,002,946 of 80-98% by weight binder, 1-10% by weight hydroxy-terminal polymethylphenylsiloxane oil, and 1-19% by weight methyl-endcapped polydiorganosiloxane oil.

[0008] Other patents deal with the improvement of the formulation, as described in U.S. Pat. No. 3,002,946. These improvements are in some cases, as described in U.S. Pat. No. 3,925,276, improvements to the silicone resin, or, as in U.S. Pat. No. 4,302,512, the improvement of the silicone oil. European Patent EP 0 239 049 describes the optimization of the catalysts in the preparation of the release coating.

[0009] The use of silicone polyesters is described in combination with laminar solids in UK Patent GB 2 152 946 A and in combination with linear siloxanes in German Patent DE 37 284 14 A.

OBJECT OF THE INVENTION

[0010] An object of the present invention is to provide a polysiloxane resin having a release effect and to provide the release coating prepared therefrom, having improved properties in respect of the release effect. The release coating must be nontoxic and easy to apply to coated or uncoated substrates.

SUMMARY OF THE INVENTION

[0011] This object is achieved by means of a composition for preparing coatings having a release effect, comprising:

[0012] (A) 100 parts by weight of one or more polysiloxane resins of the general formula

R_(a)Si(OR′)_(b)O_((4-a-b)/2)

[0013] where 0<a<2, 0<b<2 and a+b<4,

[0014] (B) from about 0.05 to about 10 parts by weight of one or more linear and/or branched polysiloxanes of the formula

R″O—[R″′₂Si—O]_(n)—R″ and

[0015] (C) from about 5 to about 80 parts by weight of a hydroxyl-containing polyester,

[0016] where

[0017] R, R′, R″ and R″′ each independently of one another are an alkyl radical, preferably having 1 to 8 carbon atoms, or an aromatic radical, preferably having 6 to 20 carbon atoms, and

[0018] n is a number in the range from 4 to 5000.

[0019] At elevated temperature, in the absence or presence of one or more solvents and judiciously using catalysts, it is possible to obtain a composition which after drying results in an improved release coating.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Component (A) (R_(a)Si(OR′)_(b)O_((4-a-b)/2)) is a polysiloxane resin where 0<a<2, 0<b<2 and a+b<4 R is an alkyl group, preferably containing 1 to 8 carbon atoms, or an aromatic group, preferably 6 to 20 carbon atoms. Examples of alkyl groups are methyl, ethyl, isopropyl, n-butyl and t-butyl. An example of an aromatic group is phenyl. Especially preferred substituents for R are methyl or phenyl or mixtures of methyl and phenyl. A preferred substituent for R′ is an alkyl group containing 1 to 8 carbon atoms, with methyl or ethyl, being especially preferred.

[0021] The preparation of silicone resins of component (A) has been known for a long time in the literature (see W. Noll in “Chemie und Technologie der Silicone”, Verlag Chemie, Weinheim (1968)) and is described, for example, in German Patent DE 34 12 648 C.

[0022] The polysiloxane (component (B)) of the formula R″O—[R″′₂Si—O]_(n)—R″ is also commonly referred to as a release oil. R″ is, for example, a hydrogen radical or an alkyl group having 1 to 8 carbon atoms. R″ can also be an —Si(CH₃)₃ group.

[0023] R″′ within the molecule of component (B) may be identical or different and may be a phenyl group or an alkyl group, preferably containing 1 to 8 carbon atoms. Especially preferred is where R″′ is methyl or phenyl or mixtures of methyl and phenyl. A small proportion of R″′ may also be a polysiloxane side chain —[R″₂Si—O]_(n)—R″, so that slightly branched structures of the release oil are possible as well as linear structures. The value for n is on average from 4 to 5000.

[0024] Likewise suitable as component (B) are pure polydimethylsiloxanes and also polydimethylsiloxanes in which up to 20 mol % of the methyl radicals have been replaced by phenyl radicals. Siloxanes of this kind have no reactive groups (R″=—Si(CH₃)₃).

[0025] The hydroxyl-containing polyester, which is described, for example, in DE 37 28 414 C1, the entire content of which is incorporated by reference, is prepared, for example, by esterification reaction from polycarboxylic acids and polyalcohols or by transesterification reaction from polycarboxylic esters with polyalcohols, with a molar ratio COOR:C—OH, or COOH:C—OH, respectively, of >1.0.

[0026] The proportions of components (A), (B) and (C) can be varied within wide ranges.

[0027] Particular preference is given, for the purposes of the present invention, to compositions containing from about 0.5 to about 5 parts by weight of polysiloxane (B), based on 100 parts by weight of component (A).

[0028] Particular preference is also given to compositions containing from about 10 to about 30 parts by weight of polyester (C), based on 100 parts by weight of component (A).

[0029] The coating compositions are preferably obtainable by reacting components (A), (B) and (C) with one another at the same time. These components are preferably only reacted up to a degree of conversion of from about 20 to about 80%, in particular from about 25 to about 80%. A sufficient degree of conversion can be determined, for example, by withdrawing a portion of the reaction mixture, drying it on a glass plate, and determining the transparency of the coating on the glass plate. A transparent film indicates a sufficient reaction conversion. The reaction conversion can be determined precisely, moreover, from the amount of ethanol distilled off.

[0030] Particularly preferred substrates that can be coated by means of the present invention are, for example, metal baking sheets, baking tins, pans, metal pots, and the like.

[0031] By baking the composition at temperatures and under conditions as described, for example, in DE 37 28 414 C1 it is possible to obtain complete reaction conversion.

[0032] The modification of the silicone resin with a polyester by transesterification reaction increases the resistance to boiling water and reduces the thermoplasticity of the cured coating. There are likewise improvements in the pigmentability and gloss of the coating.

[0033] Judiciously, the reaction is conducted at a temperature higher than room temperature using a catalyst. Suitable catalysts, as described in EP 0 092 701 A, are, for example, metal catalysts based, for example, on magnesium, cobalt, iron, aluminum, titanium, lead, zinc or tin, in the form, for example, of their laurates, octoates, acetates, acetylacetonates, neodecanoates or naphthalates. Examples of particularly suitable organotin catalysts are dibutyltin dilaurate, dibutyltin diooctoate and dibutyltin diacetate. Examples of particularly suitable organotitanium catalysts are tetra(n-butyl)titanate and tetra(isopropyl)titanate.

[0034] It has surprisingly been found that by chemical attachment of polysiloxane resin (A) and polysiloxane (B) by reaction with a hydroxy-functional polyester (C) it is possible to achieve a marked improvement in the resistance of the coating in comparison to commercially customary blends of silicone resin or silicone polyester resin with a polysiloxane (release oil) (B). Silicone polyester resins of this kind are normally prepared by reacting silicone resin (A) and polyester (C). There was likewise a decisive increase in the compatibility of silicone resin (A) and polysiloxane (B) as a result of the chemical attachment. The separation tendency of the polysiloxane (B) is markedly reduced by this means.

[0035] The compositions can be applied to the substrate in question by knife coating, dipping or spraying and lead after the baking process to a coating having an outstanding release effect.

[0036] If desired, colored coating compositions can be obtained by formulating with pigments. Additives selected from the group consisting of solvents, fillers, pigments, adhesion promoters, rheology control agents, stabilizers and additives allow the formulation to be adapted to the particular mode of application. Through the incorporation of PTFE (polytetrafluoroethylene) powder it is possible, for example, to improve the release effect further.

[0037] The invention is illustrated by the following examples.

WORKING EXAMPLES Reference Example 1 Preparation of the Silicone Resin (A)

[0038] The alkoxypolysiloxane of the formula (C₆H₅)₀ ₄₅(CH₃)₀ ₆₅—Si(OC₂H₅)0.28O_(1.31) (A) is described in DE 37 28 414 C and was prepared in accordance with DE 34 12 648 A from phenyltrichlorosilane, methylethoxypolysiloxane, ethanol and water. The silicone resin had an ethoxy content of 11.9% by weight.

Example 1 Composition of the Invention

[0039] 263 g of a hydroxyl-containing polyester (C) having an OH number of 560 mg KOH/g (prepared from trimethylolpropane and dimethyl terephthalate with catalysis in accordance with Example 1.1 from DE 37 28 414 A) was reacted with 1000 g of the silicone resin (A) from Reference Example 1 and 2.5 g of a polydimethylsiloxane (B) of the formula C₂H₅O—[Si(CH₃)₂O]₃₀—C₂H₅ in 781 g of xylene, 381 g of diethylene glycol dimethyl ether and 0.3 g of tetra(n-butyl)titanate at 135° C. to a reaction conversion at which the composition, when dried on a glass plate, gave a clear, transparent coating. The amount of ethanol removed by distillation, 74 g, corresponded to a reaction conversion of 60%.

Example 2 Composition of the Invention

[0040] 263 g of a hydroxyl-containing polyester (C) having an OH number of 560 mg KOH/g (prepared from trimethylolpropane and dimethyl terephthalate with catalysis in accordance with Example 1.1 from DE 37 28 414 A) was reacted with 1000 g of the silicone resin (A) from Reference Example 1 and 2.5 g of a polydimethylsiloxane (B) of the formula

[0041] in 781 g of xylene, 381 g of diethylene glycol dimethyl ether and 0.3 g of tetra(n-butyl)titanate at 135° C. to a reaction conversion at which the composition, when dried on a glass plate, gave a clear, transparent coating. The amount of ethanol removed by distillation, 74 g, corresponded to a reaction conversion of 60%.

Comparative Example 1 Noninventive Composition

[0042] 263 g of a hydroxyl-containing polyester (C) having an OH number of 560 mg KOH/g (prepared from trimethylolpropane and dimethyl terephthalate with catalysis in accordance with DE 37 28 414 A) was reacted with 1000 g of the silicone resin (A) from Reference Example 1 in 781 g of xylene, 381 g of diethylene glycol dimethyl ether and 0.3 g of tetra(n-butyl)titanate at 135° C. to a reaction conversion at which the composition, when dried on a glass plate, gave a clear, transparent coating. The amount of ethanol removed by distillation, 73 g, corresponded to a reaction conversion of 60%. Subsequently added to the silicone polyester resin were 2.2 g of a polydimethylsiloxane (B) of the formula C₂H₅O—[Si(CH₃)₂O]₃₀—C₂H₅, and 5 g of tetra(n-butyl)titanate were added. The formulation corresponded to formulation Z--1 from DE 37 28 414 C.

Comparative Example 2

[0043] A mixture of methylphenylsilicone resin and polydiorganosiloxane in accordance with Example 1 of EP0 239 049 C.

Example 2 Preparation of the Coatings

[0044] The compositions were prepared by mixing the components as in Table 1. TABLE 1 Formulation of the compositions (in amounts by weight) Coating 1 Coating 2 Coating 3 Coating 4 Composition as per 500 g Example 1 Composition as per 500 g Example 2 Composition as per 500 g Compar. Ex. 1 Composition as per 500 g Compar. Ex. 2 Xylene 100 g

[0045] The coatings were applied by knife coating with a dry film thickness of from about 20 to 25 μm and were baked at 280° C. for 15 minutes. Each of the films obtained was homogeneous.

[0046] Test Methods:

[0047] Release Effect:

[0048] The release effect was determined by baking a commercially customary baking mixture for cakes on the aluminum sheet coated with the compositions. The ease of removal of the cake after baking was evaluated:

[0049] 0: no cake adhesion

[0050] 1: slight cake adhesion

[0051] 2: cake difficult to remove

[0052] 3: cake largely remains adhering to the coating.

[0053] The stability of the release effect was tested by repeating the operation 100 times.

[0054] Boiling Water Test:

[0055] An aluminum sheet coated with the composition (20 μm) was immersed for 8 hours in a container filled with boiling water. Following removal from the boiling water, the coating was examined for adhesion and blistering. The adhesion test was carried out by cross-cutting in accordance with DIN ISO 2409. The evaluation was made in accordance with the following ratings:

[0056] 0: no effect after exposure

[0057] 1: slight blistering and/or slight loss of adhesion

[0058] 2: severe blistering and/or severe loss of adhesion.

[0059] Temperature Stability:

[0060] The temperature stability was determined by storage at 220° C. for a period of 16 hours. The parameters examined were the yellowing resistance (Δb in the L a b system), adhesion, and gloss retention. The adhesion test was carried out by cross-cutting in accordance with DIN ISO 2409. The evaluation was made in accordance with the following ratings:

[0061] 0: no effect as a result of temperature exposure

[0062] 1: slight yellowing and/or slight loss of adhesion after temperature exposure

[0063] 2: severe yellowing and/or severe loss of adhesion after temperature exposure.

[0064] Storage Stability:

[0065] In determining the storage stability after 4 weeks at 40° C., the parameters assessed were stability of viscosity, clouding, separation phenomena and processability.

[0066] Adhesion:

[0067] The adhesion test was carried out by cross-cutting in accordance with DIN ISO 2409.

[0068] Pencil Hardness:

[0069] The pencil hardness was determined in accordance with ECCA Standard T4-ISO 3270-ASTM D 3363.

[0070] The advantages of the coatings of the invention become clear from the tests conducted (Table 2). TABLE 2 Properties of the coatings tested: Coating 1 Coating 2 Coating 3 Coating 4 Storage stability liquid sat. sat. unsat. unsat. coating (4 weeks at (sepa- (sepa- 40° C.) ration) ration) Release effect 0 0 0 0 Release effect after 0-1 0 2 1 100 cycles Boiling water resistance 0 0 0 3 Pencil hardness at room 5H 5H 5H H temperature: at 200° C.: 4H 4H 4H 2B Gloss at 60° C. 90/88 92/91 92/82 85/72 (before/after 100 cycles) Temperature stability at 0 0 0 0 220° C., 30 hours Substrate adhesion sat. sat. sat. sat.

[0071] (where (un-)sat.=(un-)satisfactory)

[0072] The above description is intended to be illustrative and not limiting. Various changes and modifications in the embodiments described herein may occur to those skilled in the art. Those changes can be made without departing from the scope and spirit of the invention. 

What is claimed is:
 1. A composition for making coatings having a release effect, comprising (A) 100 parts by weight of one or more polysiloxane resins of the general formula R_(a)Si(OR′)_(b)O_((4-a-b)/2) where 0<a<2, 0<b<2 and a+b<4, (B) from about 0.05 to about 10 parts by weight, based upon 100 parts by weight of component (A), of one or more linear and/or branched polysiloxanes of the formula R″O—[R″′₂Si—O]_(n)—R″ and (C) from about 5 to about 80 parts by weight, based upon 100 parts by weight of component (B), of a hydroxyl-containing polyester, where R, R′, R″ and R″′ each independently of one another are an alkyl or an aromatic radical, and n is a number in the range from 4 to
 5000. 2. The composition as claimed in claim 1, which comprises (A) 100 parts by weight of one or more polysiloxane resins of the general formula R_(a)Si(OR′)_(b)O_((4-a-b)/2) where 0<a<2, 0<b<2 and a+b<4, (B) from 0.05 to 10 parts by weight of one or more linear and/or branched polysiloxanes of the formula R″O—[R″′₂Si—O]_(n)—R″ and (C) from 5 to 80 parts by weight of a hydroxyl-containing polyester, where R_(a), R′, R″ and R″′ each independently of one another are an alkyl radical having 1 to 8 carbon atoms or an aromatic radical having 6 to 20 carbon atoms, and n is a number in the range from 4 to
 5000. 3. The composition as claimed in claim 1, wherein the radicals R, R′, R″ and R″′ each independently of one another are a radical selected from methyl, ethyl, isopropyl, n-butyl, t-butyl and phenyl.
 4. The composition as claimed in claim 1, wherein the radical R″ is a hydrogen radical or a —Si(CH₃)₃ group.
 5. The composition as claimed in claim 1, wherein the radical R″′ is a polysiloxane side chain of the general formula —[R″₂Si—O]_(n)—R″.
 6. The composition as claimed in claim 1, containing from about 0.1 to about 5 parts by weight of polysiloxane (B).
 7. The composition as claimed in claim 1, containing from about 10 to about 30 parts by weight of polyester (C).
 9. The composition as claimed in claim 1, further comprising an esterification catalyst.
 10. The composition as claimed in claim 1, further comprising pigments, rheology control agents, fillers, solvents, additives, adhesion promoters and/or stabilizers.
 11. A coating composition having release effect obtainable by reacting the components (A), (B) and (C) of the composition as claimed in claim
 1. 12. The coating composition according to claim 11, wherein the components are reacted simultaneously.
 13. The composition as claimed in claim 12, wherein the degree of conversion is from about 20 to about 80%.
 14. The composition as claimed in claim 13, wherein the degree of conversion is from about 25 to about 40%.
 15. An article, coated with a coating composition as claimed in claim
 11. 16. The article as claimed in claim 17, wherein the article is a metal baking sheet, baking tin, pan or metal pot.
 17. The article as claimed in claim 15, wherein the conversion of the composition is complete.
 18. A process for preparing a composition as claimed in claim 1, which comprises reacting components (A), (B) and (C) in the presence of a catalyst and, optionally, at least one solvent.
 19. The process according to claim 18, wherein the catalyst is a metal catalyst.
 20. The process as claimed in claim 19, wherein the catalyst an organotitanium catalyst.
 21. The process as claimed in claim 19, wherein components (A), (B) and (C) are reacted in the presence of one or more solvents.
 22. The process as claimed in claim 18, wherein reaction is carried out up to a reaction conversion at which the dried composition gives a clear, transparent film. 